Pillared and open-framework uranyl diphosphonates

Journal Article · Thu Sep 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.06.039· OSTI ID:21580261

Adelani, Pius O ^[1]

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1. Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States)

The hydrothermal reactions of uranium trioxide, uranyl acetate, or uranyl nitrate with 1,4-benzenebisphosphonic acid in the presence of very small amount of HF at 200 deg. C results in the formation of three different uranyl diphosphonate compounds, [H{sub 3}O]{sub 2}{l_brace}(UO{sub 2}){sub 6}[C{sub 6}H{sub 4}(PO{sub 3})(PO{sub 2}OH)]{sub 2}[C{sub 6}H{sub 4}(PO{sub 2}OH){sub 2}]{sub 2}[C{sub 6}H{sub 4}(PO{sub 3}){sub 2}]{r_brace}(H{sub 2}O){sub 2} (Ubbp-1), [H{sub 3}O]{sub 4}{l_brace}(UO{sub 2}){sub 4}[C{sub 6}H{sub 4}(PO{sub 3}){sub 2}]{sub 2}F{sub 4}{r_brace}.H{sub 2}O (Ubbp-2), and {l_brace}(UO{sub 2})[C{sub 6}H{sub 2}F{sub 2}(PO{sub 2}OH){sub 2}(H{sub 2}O){r_brace}{sub 2}.H{sub 2}O (Ubbp-3). The crystal structures of these compounds were determined by single crystal X-ray diffraction experiments. Ubbp-1 consists of UO{sub 7} pentagonal bipyramids that are bridged by the phosphonate moieties to form a three-dimensional pillared structure. Ubbp-2 is composed of UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged through the phosphonate oxygen atoms into one-dimensional chains that are cross-linked by the phenyl spacers into a pillared structure. The structure of Ubbp-3 is a three-dimensional open-framework with large channels containing water molecules with internal dimensions of approximately 10.9x10.9 A. Ubbp-1 and Ubbp-2 fluoresce at room temperature. - Graphical Abstract: Illustration of the three-dimensional open-framework structure of {l_brace}(UO{sub 2})[C{sub 6}H{sub 2}F{sub 2}(PO{sub 2}OH){sub 2}(H{sub 2}O){r_brace}{sub 2}.H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} units, pentagonal bipyramids=green, oxygen=red, phosphorus=magenta, carbon=black, hydrogen=white. Highlights: > The influence of the uranyl salt anions and pH were critically examined in relation to structural variation. > The acetate and nitrate counter ions of uranyl may be acting as structure directing agents. > The use of rigid phenyl spacer yield a three-dimensional network of pillared structures of uranyl diphosphonates that fluoresce. > The fluorination of the phenyl ring under hydrothermal condition. > The large voids in this structure are suggestive of potential applications in sorption, separation of gases and in catalytic processes.

• OSTI ID: 21580261
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 9; Other Information: DOI: 10.1016/j.jssc.2011.06.039; PII: S0022-4596(11)00367-7; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CATALYSIS
CRYSTAL STRUCTURE
HYDROTHERMAL SYNTHESIS
MONOCRYSTALS
PHOSPHONATES
URANIUM DIOXIDE
URANIUM TRIOXIDE
URANYL NITRATES
WATER
X-RAY DIFFRACTION
ACTINIDE COMPOUNDS
CHALCOGENIDES
COHERENT SCATTERING
CRYSTALS
DIFFRACTION
HYDROGEN COMPOUNDS
NITRATES
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SCATTERING
SYNTHESIS
URANIUM COMPOUNDS
URANIUM OXIDES
URANYL COMPOUNDS